JP2023053873A - decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which has excellent three-dimensional feeling by an internal uneven shape.

SOLUTION: A decorative sheet has a transparent resin film layer having an uneven shape on one surface, and a decorative layer formed along the uneven shape of the transparent resin film layer, wherein the uneven shape has a plurality of projections different in height projecting to the side of the decorative layer from the side of the transparent resin film layer, and each of the plurality of projections has a ratio (h/w) of a height (μm) to a width w (μm) of 100% or less.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

TECHNICAL FIELD The present disclosure relates to a decorative sheet and a decorative resin molded product using the same.

2. Description of the Related Art Conventionally, decorative resin molded products obtained by laminating a decorative sheet on the surface of a resin molded product have been used for interior and exterior parts of vehicles, interior materials for building materials, housings of home electric appliances, and the like. In the production of such a decorative resin molded product, a molding method is used in which a decorative sheet having a design provided in advance is integrated with a resin by injection molding. As a representative example of such a molding method, a decorative sheet is previously formed into a three-dimensional shape using a vacuum forming mold, the decorative sheet is inserted into an injection mold, and a fluid resin is injected into the mold. The insert molding method, which integrates the resin and the decorative sheet by means of injection molding, and the simultaneous injection molding method, which integrates the decorative sheet inserted into the mold during injection molding, with the molten resin injected into the cavity. A decoration method is mentioned.

For example, by providing a printed layer on the back side of the acrylic film positioned on the surface of the decorative sheet and forming an uneven shape on the printed layer side, a decorative sheet expressing a three-dimensional shape exists inside the decorative sheet. there is In such a decorative sheet, the detailed lines and shadows of the concave-convex shape produce a sense of authenticity and a sense of luxury compared to a pattern representation by simple printing.

In recent years, however, the demand for decorative sheet designs has grown to include artificial geometric patterns and layered textures, in addition to natural objects such as real carbon and hairline, and the production of authenticity that imitates natural objects. , there is a demand for a more advanced three-dimensional effect.

JP 2010-82912 A

A main object of the present disclosure is to provide a decorative sheet that has an excellent three-dimensional effect due to the concave and convex shape inside. A further object of the present disclosure is to provide a decorative resin molded product using the decorative sheet.

The inventors of the present disclosure conducted extensive studies to solve the above problems. As a result, in a decorative sheet including a transparent resin film layer having an uneven shape on one surface and a decorative layer formed along the uneven shape of the transparent resin film layer, the uneven shape is formed on the transparent resin film layer side. A plurality of protrusions with different heights protruding from the decorative layer side, and further, for each of the plurality of protrusions, the ratio of height h (μm) to width w (μm) (h / w ) is set to 100% or less, an excellent three-dimensional effect is exhibited by the uneven shape inside the decorative sheet. The present disclosure has been completed through further studies based on such findings.

That is, the present disclosure provides inventions in the following aspects.
Section 1. a transparent resin film layer having an uneven shape on one surface;
a decorative layer formed along the uneven shape of the transparent resin film layer;
A decorative sheet comprising
The uneven shape has a plurality of protrusions with different heights protruding from the transparent resin film layer side to the decorative layer side,
The decorative sheet, wherein each of the plurality of protrusions has a ratio (h/w) of height h (μm) to width w (μm) of 100% or less.
Section 2. Item 2. The decorative sheet according to Item 1, further comprising a support film layer on the decorative layer side.
Item 3. Item 3. The decorative sheet according to Item 2, wherein the support film layer is formed so as to fill the concave portion on the decorative layer side.
Section 4. Item 4. The decorative sheet according to Item 2 or 3, further comprising an adhesive layer between the decorative layer and the support film layer.
Item 5. 5. The decorative sheet according to any one of Items 1 to 4, wherein the surface of the transparent resin film layer opposite to the decorative layer is smooth.
Item 6. a transparent resin film layer having an uneven shape on one surface;
a decorative layer formed along the uneven shape of the transparent resin film layer;
a molded resin layer;
A decorative resin molded product comprising
The uneven shape has a plurality of protrusions with different heights protruding from the transparent resin film layer side to the decorative layer side,
A decorative resin molded product, wherein each of the plurality of protrusions has a ratio (h/w) of height h (μm) to width w (μm) of 100% or less.

According to the present disclosure, it is possible to provide a decorative sheet having an excellent three-dimensional effect due to the concave and convex shape inside. Further, according to the present disclosure, it is possible to provide a decorative resin molded product using the decorative sheet.

1 is a schematic diagram of a cross-sectional structure of one form of a decorative sheet of the present disclosure; FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a decorative sheet of the present disclosure; FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a decorative sheet of the present disclosure; FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a decorative sheet of the present disclosure; FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a decorative sheet of the present disclosure; FIG. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded product of this disclosure.

1. Decorative sheet The decorative sheet of the present disclosure is a decorative sheet comprising a transparent resin film layer having an uneven shape on one surface, and a decorative layer formed along the uneven shape of the transparent resin film layer. The uneven shape has a plurality of protrusions with different heights projecting from the transparent resin film layer side to the decorative layer side, and the plurality of protrusions each have a width w (μm). The ratio (h/w) of the height h (μm) to the height is 100% or less. By having such a configuration, the decorative sheet of the present disclosure exhibits an excellent three-dimensional effect due to the concave and convex shape inside. The decorative sheet of the present disclosure will be described in detail below.

Laminated Structure of Decorative Sheet As shown in FIG. 1, a decorative sheet 10 of the present disclosure includes at least a transparent resin film layer 1 and a decorative layer 2 . The transparent resin film layer 1 has an uneven shape on one surface. The decorative layer 2 is formed along the uneven shape of the transparent resin film layer 1 . That is, the surface of the decoration layer 2 opposite to the transparent resin film layer 1 has an uneven shape. The surface of the transparent resin film layer 1 opposite to the uneven surface is preferably smooth.

The decorative sheet 10 of the present disclosure may optionally include a support film layer 3 on the decorative layer 2 side for the purpose of improving shape retention. The support film layer 3 may be formed so as to fill the uneven recesses on the decorative layer 2 side. The recess may be entirely filled with the support film layer 3, or a part of the recess may be filled with the support film layer 3, and the gap between the support film layer 3 and the uneven shape on the decorative layer 2 side may be reduced. There may be voids in

Moreover, in the decorative sheet 10 of the present disclosure, an adhesive layer 4 may be provided between the decorative layer 2 and the support film layer 3 as necessary. Although not shown, an adhesive layer may be provided on the surface of the support film layer 3 opposite to the decorative layer 2 side, if necessary.

As the laminated structure of the decorative sheet of the present disclosure, a laminated structure in which a transparent resin film layer/decorative layer are laminated in this order; a laminated structure in which a transparent resin film layer/decorative layer/support film layer are laminated in this order; a transparent resin film A laminated structure in which layer/decorative layer/adhesive layer/supporting film layer are laminated in this order; a laminated structure in which transparent resin film layer/decorative layer/adhesive layer/supporting film layer/adhesive layer are laminated in this order; 1 and 2 show schematic diagrams of cross-sectional structures of one embodiment of a decorative sheet in which a transparent resin film layer/decorative layer are laminated, as one embodiment of the laminated structure of the decorative sheet of the present disclosure. 3 and 4 are schematic diagrams of cross-sectional structures of one embodiment of a decorative sheet in which a transparent resin film layer/decorative layer/support film layer are laminated in this order, as one embodiment of the laminated structure of the decorative sheet of the present disclosure. indicates FIG. 5 is a schematic diagram of a cross-sectional structure of one embodiment of a decorative sheet in which a transparent resin film layer/decorative layer/adhesive layer/support film layer are laminated in this order, as one embodiment of the laminated structure of the decorative sheet of the present disclosure. indicates

Concavo-convex shape of decorative sheet The decorative sheet 10 of the present disclosure includes a transparent resin film layer 1 having a concavo-convex shape on one surface, and a decorative layer 2 formed along the concavo-convex shape of the transparent resin film layer 1. I have. That is, the uneven shape formed at the interface between the transparent resin film layer 1 and the decorative layer 2 constitutes the uneven shape inside the decorative sheet. When the decorative sheet of the present disclosure is observed from the side of the transparent resin film layer 1 (that is, the side viewed when the decorative sheet 10 is laminated with the molded resin layer 5 to form the decorative resin molded product 20), , the uneven shape can be visually recognized through the transparent resin film layer 1, and a high three-dimensional effect can be felt.

In the present disclosure, the concave-convex shape of the transparent resin film layer 1 includes a plurality of convex portions 1a with different heights, which protrude from the transparent resin film layer 1 side toward the decorative layer 2 side. Here, the plurality of protrusions 1a having different heights specifically means that a plurality of protrusions having heights different by 5 μm or more are provided. In the uneven shape, the ratio (h/w) of the height h (μm) to the width w (μm) of each of the plurality of projections 1a is 100% or less. That is, in the decorative sheet of the present disclosure, for the uneven shape of the transparent resin film layer 1 formed inside the decorative sheet, after forming a plurality of convex portions 1a having different heights, the convex portions By reducing the ratio (h/w) of the height h to the width w of , the uneven shape can be visually recognized from various angles, and an excellent three-dimensional effect can be felt.

From the viewpoint of more suitably exhibiting the effects of the present disclosure, the ratio (h/w) is preferably about 10 to 100%, more preferably about 20 to 60%.

For example, as shown in the schematic diagrams of FIGS. 1 to 6, the height h of each convex portion 1a is measured from the position of the concave portion 1b (line B) in the cross section of the transparent resin film layer 1 of the decorative sheet 10 in the thickness direction. It is obtained by measuring the difference (distance) from the highest position of the convex portion 1a. For example, as shown in FIG. 2, in the cross section of the decorative sheet in the thickness direction, when the heights of both ends of the convex portion 1a of the transparent resin film layer are different (line B1 and line B2), the height h to adopt. Further, as shown in FIG. 2, when a plurality of convex portions 1a with different heights are combined to form one convex portion 1a with different heights, a height h having a large value is adopted. do. In addition, for a plurality of protrusions, three or more points on the cross section are measured and evaluated.

From the viewpoint of exhibiting the effect of the present disclosure more preferably, the height h of the convex portion 1a is preferably about 3 to 100 μm, more preferably about 8 to 60 μm.

Further, from the viewpoint of more preferably exhibiting the effects of the present disclosure, the width w of the convex portion 1a is preferably about 30 to 500 μm, more preferably about 100 to 300 μm.

Further, from the viewpoint of exhibiting the effect of the present disclosure more preferably, the width x between the convex portions 1a is preferably about 3 to 200 μm, more preferably about 10 to 150 μm. The width x between the convex portions is the distance from the convex portions located on both sides of the convex portion 1a whose height h and width w are measured, and the smaller value is adopted.

In the decorative sheet of the present disclosure, the design represented by the concave-convex shape of the transparent resin film layer 1 formed inside is not particularly limited, but for example, a stripe pattern, a carbon pattern, and the like are particularly suitable.

In the decorative sheet of the present disclosure, the uneven shape may be formed in at least a part of the region that imparts a high three-dimensional effect due to the uneven shape when the decorative sheet is observed from the transparent resin film layer 1 . That is, in the decorative sheet of the present disclosure, an uneven shape that satisfies the above relationship may be formed in a part of the area or may be formed in the entire area.

Composition of each layer forming the decorative sheet [transparent resin film layer 1]
In the decorative sheet 10 of the present disclosure, the transparent resin film layer 1 is usually a layer provided so as to be located on the outermost surface of the decorative sheet 10 and the decorative resin molded product 20 . From the viewpoint of enhancing the moldability of the decorative sheet 10 of the present disclosure, the material for the transparent resin film layer 1 is preferably a thermoplastic resin. In addition, since the decorative resin molded product using the decorative sheet of the present disclosure is observed from the transparent resin film layer 1 side, the transparent resin film layer 1 is required to have transparency. The term "transparency" as used herein includes semi-transparency to the extent that the uneven shape can be seen through the transparent resin film layer 1, and colored transparency.

The transparent resin film layer 1 has an uneven shape on one surface. As will be described later, the uneven shape is formed by embossing. For example, by laminating the transparent resin film layer 1 and the decoration layer 2 and applying embossing from the decoration layer 2 side, it is possible to form an uneven shape from the decoration layer 2 to the transparent resin film layer 1 .

The thermoplastic resin used for the transparent resin film layer 1 includes acrylic resin, vinyl chloride resin, ABS resin (acrylonitrile-styrene-butadiene copolymer), styrene resin, polycarbonate resin, polyethylene terephthalate, moldable polyester resin. Polyolefin resins such as polyester resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymers, propylene-butene copolymers, and olefinic thermoplastic elastomers are preferred. Among these, acrylic resins and polyester resins are more preferable, and acrylic resins are particularly preferable. The thermoplastic resin may be used singly or in combination of two or more.

Examples of acrylic resins include acrylic resins such as polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and methyl (meth) acrylate-styrene copolymer. are used alone or in combination of two or more. In the present disclosure, (meth)acrylate means acrylate or methacrylate.

Moreover, polyester-based thermoplastic elastomers, amorphous polyesters, and the like can be used as polyester resins. Examples of the above polyester-based thermoplastic elastomers include block polymers using aromatic polyesters with high crystallinity and high melting points in the hard segments, and amorphous polyethers with a glass transition temperature of −70° C. or lower in the soft segments. Polybutylene terephthalate, for example, is used as the highly crystalline, high-melting aromatic polyester, and polytetramethylene glycol, etc., is used as the amorphous polyether. A typical example of the amorphous polyester is ethylene glycol-1,4-cyclohexanedimethanol-terephthalic acid copolymer.

As the transparent resin film layer 1, for example, a single-layer or multi-layer resin film made of the above resins can be used. In addition, various additives such as stabilizers, plasticizers, colorants, ultraviolet absorbers, hindered amine light stabilizers, and extender pigments may be added to the transparent resin film layer 1 as necessary for adjusting physical properties. may be added. These additives may be used singly or in combination of two or more. In addition, the transparent resin film layer 1 may be colored as long as the transparency is not impaired. For coloring the transparent resin film layer 1, for example, known coloring agents exemplified for the decorative layer 2 described later can be used.

The thickness of the transparent resin film layer 1 (the total thickness in the case of multiple layers) is not particularly limited, but is preferably 30 from the viewpoints of cost, performance required for the decorative resin molded product, moldability of the decorative sheet, and the like. It is preferably about to 300 μm, more preferably about 100 to 200 μm. In addition, the thickness of the transparent resin film layer 1 refers to the thickness of the portion where the uneven recesses are not formed.

The surface, the back surface, or both the front and back surfaces of the transparent resin film layer 1 may be treated with corona discharge treatment, plasma treatment, urethane resin, or the like as necessary to improve adhesion with other layers in contact with the transparent resin film layer 1. A known easy-adhesion treatment such as formation of a primer layer may be applied.

In addition, at least part of the surface of the transparent resin film layer 1 opposite to the decorative layer 2 side may be coated with a coating material as necessary for the purpose of improving the surface physical properties of the decorative sheet or providing a matte design. Moreover, a surface protective layer (not shown) may be further provided.

The resin for forming the surface protective layer is not particularly limited, and examples thereof include thermosetting resins, ionizing radiation curable resins, and thermoplastic resins. A specific example of the resin forming the surface protective layer is a two-component curing type resin and a matte coating agent containing a delustering agent. Here, as the two-component curable resin, a two-component curable resin of polyol and isocyanate is preferable.

As the polyol, there are various polyols such as acrylic polyol, polyester polyol and epoxy polyol, and acrylic polyol is preferable. Examples of the acrylic polyol include vinyl chloride-modified acrylic polyol, vinyl chloride-vinyl acetate-modified acrylic polyol, chlorinated polyolefin-modified acrylic polyol, methyl (meth) acrylate-2-hydroxyethyl (meth) acrylate copolymer, and octyl (meth) acrylate. -ethylhexyl (meth) acrylate-2 hydroxyethyl (meth) acrylate copolymer, methyl (meth) acrylate-butyl (meth) acrylate-2 hydroxyethyl (meth) acrylate-styrene copolymer, vinyl chloride Modified acrylic polyols are particularly preferred.

As the isocyanate, a conventionally known compound may be appropriately used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and other aliphatic (or alicyclic) isocyanates. Alternatively, adducts or polymers of these various isocyanates, for example, adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and the like are also used.

The matting agent used in the matte coating agent is not particularly limited, but examples include inorganic substances such as silica, alumina, calcium carbonate, aluminosilicate, barium sulfate, acrylic beads, polyethylene, urethane resin, polycarbonate, and polyamide (nylon). Particles made of organic polymers such as are used. The average particle diameter of the particles is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm, and the amount added is preferably 2 to 40% by mass, more preferably 2 to 40% by mass based on the matte coating agent (excluding the solvent content). is 5 to 30% by mass. The shape of the particles may be polyhedral, spherical, scaly, or the like. Among the above inorganic or organic particles, silica is preferred.

Moreover, as the matting agent, one having transparency is preferable. Examples of such matting agents include inorganic matting agents made of particles such as silica, spherical silica, alumina, kaolinite, calcium carbonate, barium sulfate, and glass, polycarbonate resins, acrylic resins, and polyamide (nylon) resins. , organic matting agents such as urea resins and silicon resins can be used. The particle shape of the matting agent is spherical, polyhedral, scaly, or the like. Also, the particle size of the matting agent is about 1 to 10 μm. The amount of the matting agent to be added may be determined according to the required low matte level. As the matting agent, it is also preferable to select a matting agent having excellent abrasion resistance since the surface protective layer is the outermost surface. Matting agents such as spherical silica, alumina, etc. are examples. The average particle size of the matting agent is usually 1 to 10 μm.

[Decoration layer 2]
In the decorative sheet of the present disclosure, the decorative layer 2 is a layer provided along the uneven shape of the transparent resin film layer in order to impart a high three-dimensional effect to the decorative sheet due to the uneven shape. For example, as shown in FIGS. 1 to 6, the decorative layer 2 is laminated along the uneven shape of the transparent resin film layer 1, and the decorative layer 2 fills the concave portions 1b of the transparent resin film layer 1. ing. The surface of the decoration layer 2 opposite to the transparent resin film layer 1 has a concave portion.

The decoration layer 2 can be formed of a pattern layer and/or a solid print layer. Although the pattern of the pattern layer is arbitrary, it can be selected according to the design expressed by the uneven shape of the transparent resin film layer 1 . In addition to the aforementioned stripe pattern and carbon pattern, the pattern layer includes, for example, wood grain, stone grain, cloth grain, sand grain, leather tie pattern, tile pattern, brick pattern, geometric patterns, characters, symbols, and the like. are used singly or in combination of two or more according to the application.

The decorative layer 2 can be formed by applying (printing) an ink composition for forming a decorative layer onto the transparent resin film layer 1 . The ink composition for forming the decorative layer comprises a binder resin, colorants such as pigments and dyes, and various additives that are appropriately added thereto. Examples of binder resins include acrylic resins, vinyl chloride-vinyl acetate copolymers, polyester resins, cellulose resins, chlorinated polypropylenes, urethane resins, and polyamide resins. A single resin or a mixture of two or more resins selected from the above is used. Binder resin may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of coloring agents include inorganic pigments such as titanium white, zinc white, carbon black, iron black, red iron oxide, chrome vermilion, cadmium red, ultramarine blue, cobalt blue, yellow lead, titanium yellow, phthalocyanine blue, and indus. Organic pigments (including dyes) such as ren blue, isoindolinone yellow, benzidine yellow, quinacridone red, polyazo red, and perylene red; Pearl luster (pearl) pigments and the like made of scale-like foil powder such as lead carbonate are used. Colorants may be used singly or in combination of two or more.

A specific example of the decorative layer 2 is a solid printed layer of metallic color.

The decorative layer 2 is formed by applying ink for forming the decorative layer onto the transparent resin film layer 1 by a printing method such as gravure printing, silk screen printing, or offset printing, or a known coating method such as roll coating. can do.

The thickness of the decoration layer 2 is not particularly limited, but is preferably about 0.5 to 20 μm, more preferably about 1 to 10 μm. The thickness of the decoration layer 2 refers to the thickness of the portion where the recessed portions of the uneven shape are not formed.

Also, the decoration layer 2 may be a metal thin film layer. Examples of metals forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. The method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above metals. In this case, the thickness of the decorative layer 2 (metal thin film layer) is not particularly limited, but from the viewpoint of enhancing the design and moldability of the decorative sheet, the optical density (OD value) is 0.6 to 1.8. degree, preferably about 0.8 to 1.5. Moreover, in order to improve adhesion with adjacent layers, an adhesive layer using a known resin may be provided on the front surface or the back surface of the metal thin film layer.

[Supporting film layer 3]
In the decorative sheet of the present disclosure, the support film layer 3 is provided on the decorative layer 2 side of the decorative sheet 10 (on the side opposite to the transparent resin film layer 1) as necessary in order to serve as a support member. layer to be provided. The decorative sheet of the present disclosure preferably has a support film layer 3 when used for manufacturing a decorated resin molded product by the insert molding method described later.

The material of the support film layer 3 is not particularly limited, but examples thereof include ABS resin, polyolefin resin, styrene resin, (meth)acrylic resin, vinyl chloride resin, polycarbonate resin and the like. A polypropylene resin is preferable as the polyolefin resin. Among these resins, ABS resin and polypropylene resin are particularly preferred. Further, when the molding resin constituting the molding resin layer 5 is ABS resin, the ABS resin is preferable, and when the molding resin is polypropylene resin, the polypropylene resin is preferable.

As shown in FIGS. 3 to 5 , in the decorative sheet of the present disclosure, the support film layer 3 may be laminated so as to fill the uneven recesses on the decorative layer 2 side. As a method of filling the concave portions with the support film layer 3, for example, a method of softening the support film layer 3 by heating and then laminating it on the surface on which the uneven shape is formed is exemplified.

In the decorative sheet 10 of the present disclosure, all of the uneven recesses on the decorative layer 2 side (the uneven recesses of the decorative layer 2, the uneven recesses of the adhesive layer 4 when the adhesive layer 4 described later is further provided, etc.) may be filled with the support film layer 3, or part of the concave portion may be filled with the support film layer 3, and a gap exists between the support film layer 3 and the uneven shape on the decorative layer 2 side. may

The thickness of the support film layer 3 is not particularly limited, and is, for example, approximately 0.1 to 0.5 mm, more preferably approximately 0.2 to 0.4 mm. The thickness of the support film layer 3 refers to the thickness of the portion of the decorative sheet 10 on the side of the decorative layer 2 that does not fill the uneven concave portions.

[Adhesion layer 4]
In the decorative sheet 10 of the present disclosure, an adhesive layer 4 may be provided between the decorative layer 2 and the support film layer 3 as necessary for the purpose of improving the adhesion between these layers. Although illustration is omitted, an adhesive layer may be provided on the surface of the support film layer 3 opposite to the decorative layer 2 side, if necessary.

In the present disclosure, when the adhesive layer 4 is provided between the decorative layer 2 and the support film layer 3, the uneven shape is formed by embossing from the side of the decorative layer 2 opposite to the transparent resin film layer 1 side. Later, an adhesive layer can be formed over the uneven shape.

Examples of materials for the adhesive that constitutes the four adhesive layers include two-component curable urethane resins using isocyanate as a curing agent, chlorinated polyolefins such as chlorinated polypropylene, (meth)acrylic resins, and vinyl chloride-vinyl acetate copolymers. and a mixture of a (meth)acrylic resin and a vinyl chloride-vinyl acetate copolymer. As the (meth)acrylic resin and vinyl chloride-vinyl acetate copolymer in the adhesive layer, the same materials as those used in the decorative layer 2 may be used. When the support film layer 3 is made of ABS resin or polyolefin resin, it is preferable to use, as the adhesive layer, a two-liquid curing type urethane resin using isocyanate as a curing agent, chlorinated polyolefin such as chlorinated polypropylene, or the like.

Moreover, the adhesive layer 4 can be formed by a known printing or coating method such as gravure printing or roll coating using the above adhesive. The thickness of the adhesive layer is not particularly limited, and is usually about 1 to 50 μm.

Embossing In the decorative sheet 10 of the present disclosure, the uneven shape of the interior described above can be formed by embossing. Specifically, a sheet having at least the transparent resin film layer 1 and the decoration layer 2 is prepared, and the sheet is embossed from the decoration layer 2 side to form an uneven shape with recesses reaching the transparent resin film layer 1 . By adjusting the plate depth of the embossing plate used for embossing, a plurality of convex portions 1a having different heights and projecting from the transparent resin film layer 1 side to the decorative layer 2 side, and the width of the plurality of convex portions 1a. It is possible to form an uneven shape in which the ratio (h/w) of height h (μm) to w (μm) is 100% or less.

As a method for embossing, an embossing method using heat and pressure is usually used. The embossing method using heat and pressure is a method in which the surface of the sheet is heated and softened, pressed with an embossing plate to form the uneven pattern of the embossing plate, and cooled to fix. The shape of the embossing plate used for embossing corresponds to the uneven shape formed on the transparent resin film layer 1 and the decorative layer 2 . For embossing, for example, a known sheet-fed or rotary embossing machine can be used.

In the embossing method using heat and pressure, for example, a method of embossing on the decorative layer 2 and a method of embossing the decorative layer along the uneven shape from above the uneven shape of the transparent resin film layer 1 having the uneven shape. There is a method of coating 2. For example, by embossing, the embossing plate reaches from the decoration layer 2 to the transparent resin film layer 1 , thereby forming recesses reaching the transparent resin film layer 1 . Specifically, a sheet having a layer including at least the decorative layer 2 and the transparent resin film layer 1 is prepared, and the decorative layer 2 is embossed to form the plurality of uneven convex portions 1a. Form a region that satisfies the ratio (h/w).

The heating temperature for embossing is not particularly limited, but is preferably about 180°C to 220°C.

Further, after embossing, the plurality of uneven convex portions 1a may adjust the ratio (h/w). For example, after the embossing step, the surface of the transparent resin film layer 1 may be mirror-finished to deform the uneven shape, thereby adjusting the ratio (h/w). The adjustment by mirror-finishing may be performed when the ratio (h/w) of the uneven convex portions 1a in the embossing is not 100% or less, or may be performed when it is 100% or less.

As described above, the surface of the transparent resin film layer 1 opposite to the uneven surface is preferably smooth, and the smoothness can be enhanced by mirror finishing. The surface of the transparent resin film layer 1 can be mirror-finished using a mirror roller or the like. Specifically, the embossed sheet can be passed between a heated mirror roller and a rubber roller to apply heat and pressure. A specular roller is pressed against the surface of the transparent resin film layer 1, and the rear side of the sheet is pressed with a rubber sheet. The mirror surface roller can be a metal roller whose surface is mirror-finished with an iron core or the like by chromium plating or the like, and the rubber roller can be a roller with an iron core or the like coated with rubber such as silicone rubber. . By pressing the mirror surface roller, the uneven shape immediately after being formed by embossing is deformed, and the ratio (h/w) can be adjusted to 100% or less. When the above ratio (h/w) is satisfied by embossing, mirror finishing may be performed without substantially changing the above ratio (h/w).

An excellent specularity can be imparted to the front side of the transparent resin film layer 1 by mirror finishing. The specularity is preferably 1 μm or less, more preferably 0.1 μm or less in terms of arithmetic mean roughness Ra according to JIS B0601 (1996). That is, the mirror-finished surface is a surface having the arithmetic mean roughness Ra of preferably 1 μm or less, more preferably 0.1 μm or less.

Further, in the present disclosure, after the embossing process, the support film 3 is laminated so as to fill the recesses of the uneven shape of the sheet so that the ratio (h / w) is 55% or less. It can also be adjusted. The method of laminating the support film layer 3 so as to fill the concave portions is as described above. Note that the adjustment of the ratio (h/w) by laminating the support film layer 3 may be performed when the ratio (h/w) of the uneven convex portions 1a is not 100% or less in the embossing. However, it may be performed when it is 100% or less. Further, when the ratio (h/w) is satisfied by embossing, the support film 3 may be laminated without substantially changing the ratio (h/w). .

Furthermore, in the present disclosure, after embossing, both the above-described mirror finishing and lamination of the support film 3 may be performed to adjust the ratio (h/w) to 100% or less. can. Specifically, after the embossing step, a step of laminating a support film so as to fill the recesses of the uneven shape of the sheet, and a step of laminating the support film, and the opposite side of the transparent resin film layer 1 on which the uneven shape is formed. It is possible to adjust the ratio (h/w) to 100% or less by performing a step of mirror-finishing the side surface. When both the mirror finishing and the lamination of the support film 3 are performed, the order is not particularly limited, but from the viewpoint of protecting the mirror surface formed by the mirror finishing, the mirror finishing is performed after the support film 3 is laminated. is preferably applied.

2. Decorative Resin Molded Product The decorative resin molded product 20 of the present disclosure is molded by integrating the decorative sheet 10 of the present disclosure and molding resin. That is, the decorative resin molded product 20 of the present disclosure includes at least a transparent resin film layer 1 having an uneven shape on one surface, a decorative layer 2 formed along the uneven shape of the transparent resin film layer 1, and a molded A decorative resin molded product including a resin layer 5, the uneven shape having a plurality of protrusions 1a with different heights that protrude from the transparent resin film layer 1 side to the decorative layer 2 side, The ratio (h/w) of the height h (μm) to the width w (μm) of each of the plurality of projections 1a is 100% or less. In addition, as described for the decorative sheet 10 of the present disclosure, the decorative resin molded product includes the support film layer 3, the adhesive layer 4, and the surface of the support film layer 3 opposite to the decorative layer 2 side. An adhesive layer or the like may be provided.

The decorative resin molded product of the present disclosure is produced, for example, using the decorative sheet of the present disclosure by various injection molding methods such as an insert molding method, an injection molding simultaneous decoration method, a blow molding method, and a gas injection molding method. be. Among these injection molding methods, the insert molding method and the simultaneous injection molding decoration method are preferred. In addition, the decorative resin molded product of the present disclosure can be obtained by a decorating method such as a vacuum pressure bonding method, in which the decorative sheet of the present disclosure is attached onto a three-dimensional resin molded body (molded resin layer) prepared in advance. can also be made.

In the insert molding method, first, in the vacuum forming process, the decorative sheet of the present disclosure is vacuum formed (offline preforming) in advance into the surface shape of the molded product using a vacuum forming mold (offline preforming), and then, if necessary, the excess portion is trimmed. Obtain a molded sheet. This molding sheet is inserted into an injection mold, the injection mold is clamped, and the resin in a fluid state is injected into the mold and solidified. A decorative resin molded product is manufactured by making it harden.

More specifically, the decorative resin molded product of the present disclosure is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming the decorative sheet of the present disclosure into a three-dimensional shape in advance with a vacuum forming mold;
A trimming process to obtain a molded sheet by trimming the excess part of the vacuum-formed decorative sheet, insert the molded sheet into the injection mold, close the injection mold, and inject the resin in a fluid state into the injection mold. An integration process that integrates the resin and the molded sheet.

In the vacuum forming step in the insert molding method, the decorative sheet may be heated and formed. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. can be to some extent. In addition, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but it is usually about 180 to 320.degree. C., preferably about 220 to 280.degree.

In the simultaneous injection molding and decorating method, the decorative sheet of the present disclosure is arranged in a female mold that is also used as a vacuum molding mold provided with injection molding suction holes, and preforming (inline preforming) is performed in this female mold. After that, the injection mold is clamped, and the resin in a fluid state is injected and filled into the mold, solidified, and the decorative sheet of the present disclosure is integrated with the outer surface of the resin molding at the same time as the injection molding. Thus, a decorative resin molded product is manufactured.

More specifically, the decorated resin molded product of the present disclosure is manufactured by the simultaneous injection molding and decorating method including the following steps.
After setting the decorative sheet of the present disclosure so that the surface of the decorative sheet opposite to the transparent resin film layer 1 faces the molding surface of a movable mold having a molding surface of a predetermined shape, Preforming for preforming the decorative sheet by heating and softening the decorative sheet and applying vacuum suction from the movable mold side to adhere the softened decorative sheet along the molding surface of the movable mold. process,
After the movable mold and fixed mold having the decorative sheet adhered along the molding surface are clamped, the resin in a fluid state is injected into the cavity formed by both molds, filled and solidified. A process of integrating the resin molded body and the decorative sheet by lamination, and a resin molding in which all layers of the decorative sheet are laminated by separating the movable mold from the fixed mold. Extraction process to take out the body.

In the preforming step of the simultaneous injection molding and decorating method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. Usually, it can be about 70 to 130°C. Also, in the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but it is usually about 180 to 320.degree. C., preferably about 220 to 280.degree.

In the vacuum crimping method, first, the decorative sheet and the resin molded body of the present disclosure are placed in a vacuum crimping machine consisting of a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side. Installed in a vacuum pressure bonding machine so that the vacuum chamber side, the resin molded body is on the second vacuum chamber side, and the side opposite to the transparent resin film layer 1 of the decorative sheet faces the resin molded body side, and the two vacuum chambers is in a vacuum state. The resin molded body is placed on a vertically movable platform provided on the side of the second vacuum chamber. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using a lifting table, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. affixed to the surface of Finally, the two vacuum chambers are opened to the atmospheric pressure, and the excess portion of the decorative sheet is trimmed as necessary to obtain the decorated resin molded product of the present disclosure.

In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve formability before the step of pressing the molding against the decorative sheet. A vacuum compression bonding method including the process is sometimes called a vacuum thermocompression bonding method. The heating temperature in this step may be appropriately selected according to the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, but it can usually be about 60 to 200.degree.

In the decorative resin molded product of the present disclosure, the molded resin layer may be formed by selecting a resin according to the application. The resin forming the molded resin layer may be a thermoplastic resin or a thermosetting resin.

Examples of thermoplastic resins include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins. These thermoplastic resins may be used singly or in combination of two or more.

Further, examples of thermosetting resins include urethane resins and epoxy resins. These thermosetting resins may be used singly or in combination of two or more.

The decorative resin molded product of the present disclosure has a high three-dimensional effect such as unevenness, three-dimensionality, and depth due to the uneven shape, and has high surface smoothness. Interior or exterior materials for vehicles; Fittings such as window frames and door frames; Interior materials for buildings such as walls, floors and ceilings; can be done.

EXAMPLES The present disclosure will be described in detail below with reference to examples and comparative examples. However, the present disclosure is not limited to the examples.

[Examples 1 to 7 and Comparative Examples 1 to 3]
<Manufacturing of decorative sheets>
As a transparent resin film layer, an acrylic film (thickness: 125 μm) with both sides smooth was prepared. An ink composition (polybutyl methacrylate/vinyl chloride-vinyl acetate copolymer) was applied to one surface of the transparent resin film layer by gravure printing to form a decorative layer (thickness: 5 μm). Next, the decorative layer was embossed using an embossing plate (which forms a stripe pattern) to form an uneven shape. In Example 6, an adhesive (polyester resin composition, polyester polyol:isocyanate=100:10) was further applied on the decorative layer by gravure printing to form an adhesive layer (thickness: 30 μm).

The plate depth of the embossing plate used in each example and comparative example is different. In Examples 1 to 7 and Comparative Example 3, the depth of the embossed plate was not uniform (the plate depth was 30 to 60 μm in Examples 1 and 4 to 9, 10 to 45 μm in Example 2, Example 3 is 5 to 30 μm), and Comparative Examples 1 and 2 have uniform plate depths (plate depth is 26 μm in Comparative Example 1 and 45 μm in Comparative Example 2). The cross section of the obtained decorative sheet was observed with a microscope, and three convex portions were randomly selected (those with a height difference of 5 μm or more) from the uneven shape formed on the transparent resin film layer. The width w (μm) of the portion, the height h (μm) of the projection, the ratio of the height h to the width w of the projection (h/w), and the width x (μm) between the projections were measured. As shown in FIG. 2, in the cross section of the decorative sheet in the thickness direction, when the heights h of both ends of the protrusions of the transparent resin film layer are different, the height h having the larger value was adopted. Also, as shown in FIG. 2, when a plurality of protrusions with different heights are combined to form one protrusion with different heights, the height h having a large value is adopted. . The width x between the convex portions is the distance from the convex portions located on both sides of the measured height h and width w, and the smaller value was adopted. Table 1 shows the results.

(Evaluation of stereoscopic effect 1)
The decorative sheet obtained above was used as a test sample and placed on a horizontal surface under a white fluorescent lamp with the transparent resin film layer facing upward. Next, the test sample was separated from the test sample by about 50 cm and visually observed from a direction of 90° (directly above) with respect to the horizontal plane, and the three-dimensional effect was evaluated according to the following evaluation criteria. Evaluation criteria are as follows.
A+: Concavo-convex shape was clearly visible, and a strong three-dimensional effect was visually observed.
A: Concavo-convex shape was visually recognized, and a three-dimensional effect was visually perceived.
B: Although the uneven shape is somewhat difficult to visually recognize, it was confirmed that the three-dimensional design due to the uneven shape was expressed.
C: Concavo-convex shape could not be confirmed.

(Evaluation of stereoscopic effect 2)
The decorative sheet obtained above was used as a test sample and placed on a horizontal surface under a white fluorescent lamp with the transparent resin film layer facing upward. Next, it was visually observed from a direction of 45° to the horizontal plane at a distance of about 50 cm from the test sample, and the three-dimensional effect was evaluated according to the following evaluation criteria. Evaluation criteria are as follows.
A+: Concavo-convex shape was clearly visible, and a strong three-dimensional effect was visually observed.
A: Concavo-convex shape was visually recognized, and a three-dimensional effect was visually perceived.
B: Although the uneven shape is somewhat difficult to visually recognize, it was confirmed that the three-dimensional design due to the uneven shape was expressed.
C: Concavo-convex shape could not be confirmed.

1 Transparent resin film layer 1a Convex portion 1b Concave portion 2 Decorative layer 3 Support film layer 4 Adhesive layer 5 Molded resin layer 10 Decorative sheet 20 Decorative resin molded article

Claims (5)

a transparent resin film layer having an uneven shape on one surface;
a decorative layer formed along the uneven shape of the transparent resin film layer;
A decorative sheet comprising
The uneven shape has a plurality of protrusions with different heights protruding from the transparent resin film layer side to the decorative layer side,
The decorative sheet, wherein each of the plurality of protrusions has a ratio (h/w) of height h (μm) to width w (μm) of 100% or less. The decorative sheet according to claim 1, further comprising a support film layer on the decorative layer side. 3. The decorative sheet according to claim 2, wherein the support film layer is formed so as to fill the concave portion on the decorative layer side. 4. The decorative sheet according to claim 2, further comprising an adhesive layer between said decorative layer and said support film layer. The decorative sheet according to any one of claims 1 to 4, wherein the surface of the transparent resin film layer opposite to the decorative layer is smooth.

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